CN112723373B - Method for synthesizing hierarchical porous NaY molecular sieve at low cost - Google Patents

Method for synthesizing hierarchical porous NaY molecular sieve at low cost Download PDF

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CN112723373B
CN112723373B CN201911030840.1A CN201911030840A CN112723373B CN 112723373 B CN112723373 B CN 112723373B CN 201911030840 A CN201911030840 A CN 201911030840A CN 112723373 B CN112723373 B CN 112723373B
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molecular sieve
stirring
nay molecular
template agent
mixed
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CN112723373A (en
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杜艳泽
方向晨
牛国兴
柳伟
黄曜
秦波
赵东元
高杭
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/24—Type Y
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B01J35/60—
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution

Abstract

The invention discloses a method for synthesizing a hierarchical pore NaY molecular sieve at low cost, wherein a mixed template agent containing amphiphilic organosilane and cationic surfactant is adopted in the synthetic process of the hierarchical pore NaY molecular sieve, and the molar ratio of the amphiphilic organosilane to the cationic surfactant in the mixed template agent is 1: (0.1 to 5), preferably 1: (2~3). The method can efficiently play the role of the template agent and synthesize the hierarchical pore NaY molecular sieve with rich mesoporous characteristics at low cost under the participation of a very small amount of the template agent.

Description

Method for synthesizing hierarchical porous NaY molecular sieve at low cost
Technical Field
The invention belongs to the technical field of material chemistry, catalytic chemistry and chemical engineering, relates to a method for synthesizing a hierarchical pore NaY molecular sieve at low cost, and particularly relates to a method for synthesizing a hierarchical pore NaY molecular sieve with regular and unobstructed mesopores at low cost.
Background
The Y molecular sieve is an important active component of a catalytic cracking catalyst and a hydrocracking catalyst all the time, but with the aggravation of crude oil heaviness, the content of polycyclic compounds and macromolecules in raw materials is remarkably increased, and the diffusion of the macromolecules in microporous Y molecular sieve pore passages with the pore diameter of only 0.74nm is severely limited, so that the activity of the catalyst is reduced, the carbon deposition is aggravated, the service life is shortened, the probability of secondary cracking reaction is increased, the selectivity is influenced, and the high-efficiency application of the Y molecular sieve in industrial catalysis is severely restricted.
The diffusion of macromolecular materials can be effectively improved by introducing multilevel holes into the Y molecular sieve crystal. It has unique catalytic activity, increased liquid yield and reduced deactivation compared with conventional microporous Y molecular sieve (Perez-Ramirez J, et a1. Chemical Society Reviews 2008, 37: 2530-42). Therefore, how to prepare the NaY molecular sieve which is beneficial to material transfer and has multi-stage pore channels becomes a research hotspot in the field of molecular sieve material synthesis, catalytic cracking and hydrocracking catalyst preparation at present.
The method for preparing the hierarchical pore Y molecular sieve has a plurality of methods, mainly comprising a post-treatment method and a soft template method and a hard template method. The post-treatment method is mainly characterized in that framework aluminum (CN 105712375A, CN103936024A, CN104096586A, CN104229823A and the like) is removed through acid or hydrothermal treatment or molecular sieve framework silicon (CN 106629766A, CN104843736A, CN107777697A, CN107973312A, CN106669774A, CN101722022, CN105712370A and the like) is etched by alkali to be introduced into mesoporous channels. In particular, the hierarchical pores generated by the destruction of the molecular sieve framework, usually of the type of "ink bottle" structure, have poor connectivity with each other, and the diffusion of macromolecules is still limited by the size of the "bottle mouth", so that this method has a limited ability to improve the performance of the catalyst. The template method is a method for constructing multi-stage pore channels by introducing various mesoporous templates, including hard templates such as activated carbon materials (CN 106809857A, CN1749161A, CN10308638A and the like) or soft templates such as surfactants (CN 107140656A, CN106608638A, CN102774854A, CN102689910A, CN107555446A, CN104760973A and the like). However, this method has many problems including low yield of the hard template method and no industrial production value; and the soft template method needs to consume a large amount of surfactant, increases the cost, and releases a large amount of waste water and waste gas when the template agent is removed, thereby seriously polluting the environment. More particularly, aiming at the synthesis of the hierarchical porous Y molecular sieve, no ideal soft template method synthesis method with industrial application value exists at present.
Although it is possible to use a single device, inayat A and the like successfully synthesize the hierarchical porous X-type molecular sieve by using 3-hexadecyl-3-diethylamino-propyltrimethoxysilylammonium bromide (TPHAC) amphiphilic organosilane as a template agentAngew. Chem. Int. Ed2012, 51 (8): 1962-1965), but we found this method to be applied to the synthesis of Y molecular sievesThe effect is not ideal, the promotion range of the mesoporous surface area and the volume of the molecular sieve is limited, and even if the dosage of the template agent is increased, the Y molecular sieve with rich mesoporous factors can not be obtained, and even the effective crystallization of the NaY molecular sieve can be prevented. Chinese patents CN102259889A and CN103214003A disclose the use of N, N-diethylamino-N-hexadecyl-N- (3-methoxypropane) ammonium iodide and N, N-dimethyl-N- [3- (trimethoxysilicon) propyl, respectively]Method for synthesizing mesoporous Y-type molecular sieve by taking octadecylammonium chloride (TPOAC) amphiphilic organosilane as Template agent, but the Template dosage used by the two methods is larger (Template/SiO) 2 >3 mol%), which undoubtedly will increase the synthesis cost of the hierarchical porous Y molecular sieve for expensive amphiphilic organosilane, and is not favorable for industrial application and popularization.
When TPHAC or TPOAC amphiphilic organosilane is used for synthesizing the hierarchical porous NaY molecular sieve, the dosage of the template agent is very important. Too much template agent will not only increase the cost, but also will aggravate the self-crosslinking of Si-O-Si between the template agent molecules and cause failure. At the same time, the presence of excess siloxane head prevents effective crystallization of the material. If the dosage of the template agent is too small, the template agent cannot well form micelles, and the effect of inducing and constructing regular mesopores is weakened. Therefore, the technical key of synthesizing the hierarchical porous NaY molecular sieve by using the amphiphilic organosilane is to solve the three problems of how to ensure the formation of a complete micelle, how to reduce the intermolecular Si-O-Si crosslinking of the template agent and how to promote the crystallization of the material under the participation of a very small amount of the amphiphilic organosilane.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for synthesizing a hierarchical pore NaY molecular sieve with rich mesoporous characteristics at low cost by efficiently playing the role of a template agent with the participation of a very small amount of the template agent.
A method for synthesizing a hierarchical porous NaY molecular sieve at low cost adopts a mixed template agent containing amphiphilic organosilane and cationic surfactant in the synthesis process, wherein the molar ratio of the amphiphilic organosilane to the cationic surfactant in the mixed template agent is 1: (0.1 to 5), preferably 1: (0.5 to 5), and more preferably 1: (1 to 4), and more preferably 1: (2-3).
In the method, the preparation process of the mixed template agent is as follows: dissolving appropriate amount of cationic surfactant in water, adding amphiphilic organosilane solution, preferably 20-50 o C, adding an amphiphilic organosilane alcohol solution (preferably a methanol solution) in a dropwise manner under the stirring condition; it is further preferred to add dropwise the entire amphiphilic organosilane solution required within 30s to 120s, and optionally to continue stirring after the end of the addition, preferably to continue stirring for 60s to 180s.
In the method, the amphiphilic organosilane is one or more of surfactants containing N, N-diethylamino (or dimethyl) -N- [ 3-trimethicone (or triethoxysilicane) propane ] chloro or bromo, quaternary ammonium iodide hydrophilic groups and C12-C24 straight chain or branched chain alkane hydrophobic groups; preferably at least one of N, N-diethyl-N- [ 3-trimethylsilylpropyl ] hexadecylammonium bromide (TPHAC), N-diethyl-N- [ 3-trimethylsilylpropane ] hexadecylammonium iodide and N, N-dimethyl-N- [ 3-trimethylsilylpropyl ] octadecylammonium chloride (TPOAC).
In the method, the cationic surfactant is a surfactant containing a quaternary ammonium salt hydrophilic group and a C12-C24 straight chain or branched chain alkane hydrophobic group, and preferably at least one of Cetyl Trimethyl Ammonium Bromide (CTAB) and Cetyl Trimethyl Ammonium Chloride (CTAC).
A method for synthesizing a hierarchical porous NaY molecular sieve at low cost specifically comprises the following steps:
(1) Firstly, uniformly mixing a silicon source, an aluminum source, an alkali source, a mixed template agent, water and a nano NaY molecular sieve seed crystal stock solution according to the calculated amount to finally form Na with the molar ratio of (0.35 to 0.5) 2 O : (0.06~0.1)Al 2 O 3 : SiO 2 0.001 to 0.01, and (20 to 70) H 2 A sol of O; the sol molar ratio is preferably (0.35 to 0.45) Na 2 O : (0.08~0.1) Al 2 O 3 : SiO 2 0.0025 to 0.004, 20 to 40 percent of H 2 O, more preferably 0.4 Na 2 O : 0.08 Al 2 O 3 : SiO 2 0.0035 mixed template agent 30H 2 O; wherein the mixed template agentThe amount is calculated by the mole number of the amphiphilic organosilane in the mixed template agent;
(2) And (2) crystallizing, filtering, washing, drying and roasting the material obtained in the step (1) to obtain the hierarchical porous NaY molecular sieve.
In the method, in the step (1), a silicon source, an aluminum source, an alkali source, a mixed template agent, a nano NaY molecular sieve seed crystal stock solution and water are further preferably uniformly mixed to form a sol, and the addition amount of the nano NaY molecular sieve seed crystal stock solution accounts for 0.1 to 10 percent, preferably 0.5 to 2 percent of the total mass of the sol system.
In the method, the composition of the mixed template agent in the step (1) is 1.0 amphiphilic organosilane, (0.1 to 5) cationic surfactant; preferably 1.0 amphiphilic organosilane (2.0 to 3.0) cationic surfactant.
The preferred mixing procedure in step (1) of the above process is as follows: all silicon sources and part of H 2 And O, fully mixing and stirring, adding the required mixed template agent once or more (preferably once), stirring until the materials are white and solid, placing the materials in a range of 0.5-2 h, adding the required aluminum source and alkaline aqueous solution, stirring for a period of time, then supplementing the balance of water, preferably stirring for a period of time, adding the nano NaY molecular sieve seed crystal stock solution, then supplementing the balance of water, preferably stirring for 12-36 hours at room temperature, adding the nano NaY molecular sieve seed crystal stock solution, and then supplementing the balance of water.
In the method, the nano NaY molecular sieve seed crystal stock solution can be prepared by adopting any one of the prior art. A specific preparation method is exemplified, which does not constitute a limitation of the present invention, and is specifically as follows: according to Na 2 O : Al 2 O 3 : SiO 2 : H 2 O = (10 to 15): 1 (10 to 18): 200 to 400, and the molar ratio of the silicon source, the aluminum source and the water is 0~5 o C, mixing in an ice water bath until the mixture is colorless and transparent, continuously stirring at room temperature for 12-36h, and then stirring at 40-80% o And C, standing and crystallizing for 6 to 96 hours to obtain semi-transparent, pale and viscous nano NaY molecular sieve seed crystal stock solution.
In the method, the silicon source in the step (1) is one or more of water glass, silica sol, silica gel and white carbon black, wherein the silica sol is preferred; the aluminum source is one or more of aluminum nitrate, aluminum sulfate, sodium metaaluminate and metal aluminum, wherein the preferred is sodium metaaluminate; the alkali source is one or more of potassium hydroxide, sodium hydroxide and ammonia water, and preferably sodium hydroxide.
In the method, the crystallization temperature in the step (2) is 80 to 100 o C, crystallizing for 12 to 96 hours; the drying temperature is 100 to 150 DEG o C, drying for 2 to 5 hours, and roasting at the temperature of 450 to 550 o And C, roasting for 2 to 4 hours.
The hierarchical porous NaY molecular sieve prepared by the method has the total specific surface area of 750-850 m 2 Per g, the total pore volume is 0.50 to 0.65 cm 3 (ii)/g; the specific surface area of the mesopores is 120 to 320 m 2 The mesoporous volume is 0.15 to 0.25 cm 3 (ii)/g; the specific surface area of the micropores is 500 to 700 m 2 The pore volume of the micropores is 0.32 to 0.38 cm 3 /g。
The low temperature N of the NaY molecular sieve synthesized by the invention 2 Adsorption on p/p 0 The position where the mark is not less than 0.4 and not more than 0.6 is obviously lifted, and the material is similar to an MCM-41 mesoporous material and presents a typical IV-type adsorption-desorption curve, wherein the p/p at the lifted position 0 The partial pressure is higher than p/p of MCM-41 0 = 0.2-0.4; the molecular sieve has a two-dimensional straight channel mesoporous structure similar to MCM-41 material, is slightly larger than the MCM-41, and is a highly crystallized mesoporous NaY molecular sieve with rich and smooth two-dimensional straight channels.
The invention relates to a novel method for promoting a small amount of amphiphilic organosilane to form a complete micelle and ensuring the stability and high dispersion of the amphiphilic organosilane in a water phase by using a 'card insertion type' mixed template method; according to the method, CTAB (cetyl trimethyl ammonium bromide) is used as a micelle promoter and is mixed with amphiphilic organosilane according to a certain proportion, and amphiphilic organosilane template molecules are 'intercalated' in complete CTAB micelles to form a 'card-inserting type' mixed template agent, so that when a small amount of amphiphilic silane template agent is used, a system can also form complete micelles, and the effect of inducing a NaY molecular sieve to form a mesoporous structure is fully exerted; meanwhile, self-crosslinking among molecules of the amphiphilic silane template agent is effectively inhibited by the obstruction of CTAB molecules, so that the utilization rate of the template agent is improved, and the using amount and the synthesis cost of the template agent are reduced.
The method uses the nano NaY molecular sieve seed crystal stock solution as a material crystallization guiding agent, is different from the conventional transparent guiding agent, and the nano NaY molecular sieve seed crystal has the capability of faster and better directionally inducing material crystallization, and can effectively counteract the barrier effect of the amphiphilic organosilane molecular siloxane terminal on the molecular sieve crystallization.
The method can synthesize the hierarchical pore Y molecular sieve with rich mesoporous characteristics, high crystallinity and good purity only by the participation of a very small amount of amphiphilic organosilane template agent, has low production cost and is beneficial to industrial production and application; the hierarchical pore Y molecular sieve prepared by the invention can be used as a catalyst or a carrier for isomerization pour point depression, hydrocracking, catalytic cracking and the like.
Drawings
FIG. 1 is an X-ray diffraction pattern of the Meso-NaY-3 synthesized in example 3 and the Ref-sample-1 synthesized in example 11.
FIG. 2 is a low temperature nitrogen sorption-desorption plot of the Meso-NaY-3 synthesized in example 3 and the Ref-sample-1 synthesized in example 11.
FIG. 3 is a graph showing the pore size distribution of Meso-NaY-3 synthesized in example 3 and Ref-sample-1 synthesized in example 11.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, deriving materials, substances, methods, steps, etc., the subject matter that is derived from the heading encompasses those conventionally used in the art as proposed in the present application, but also includes those that are not currently in use, but would become known in the art to be suitable for a similar purpose.
The X-ray diffraction pattern in this example was measured by Bruker D4 powder diffractometer, cuK α The source, tube pressure 40 kV, tube flow 40 mA.
The low-temperature nitrogen adsorption-desorption curve of the molecular sieve is measured in a Micromeritics Tristar 3020 type analyzer at 77K, and the BET method is used for calculating the specific surface area of a sample.
The pore size distribution curve of the molecular sieve of this example was measured at 77K on a Micromeritics Tristar 3020 analyzer, the pore size distribution was calculated by the BJH method, the pore volume was calculated from the adsorption at a relative pressure of 0.995, and the micropores were analyzed by the t-plot method.
Example 1
1. And (3) synthesis of nano NaY molecular sieve seed crystal:
200 Dissolving NaOH in 500 g water, cooling, slowly adding 37.80 g metal aluminum wires for multiple times, supplementing water loss after completely dissolving, and cooling to room temperature for use (solution A); 520 g NaOH was dissolved in 980 g water, 2000 g was added containing 30% SiO 2 Heating and stirring the silica sol properly, cooling the solution to 0~5 by using an ice water bath after the solution becomes transparent and no particles are determined o C, adding the solution (A) prepared before one time, stirring to obtain a colorless transparent solution, stirring at room temperature for 24 h, and then 60 o C standing and crystallizing 24 h to obtain pale white semitransparent viscous emulsion. The final composition of the liquid crystal is as follows: 12.9 Na (Na) 2 O : Al 2 O 3 : 14.3 SiO 2 : 229 H 2 O。
2. Synthesizing a hierarchical porous NaY molecular sieve:
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; then 0.238 g CTAB was added at 40 o Dissolving in 10.0 g of H under C 2 In O, under the temperature and stirring, 0.269 g TPHAC methanol solution with the concentration of 0.4382 g/g is dripped in 1 min, after 2 min of stirring, the TPHAC methanol solution is added into the silica sol system which is dispersed before, the mixture is quickly stirred for 10 min, the material is in a white solidification state, after 1 h is placed, 3.478 g NaAlO is added 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) and 4.840 g NaOH in 56.33 g H 2 Solution of O at room temperature (-25 ~) o C) Stirring 24 h, adding nano NaY molecular sieve seed crystal stock solution with total crystallized material mass fraction of 1.64% (2.31 g), stirring 4 h at room temperature, and 90 o C crystallized 46 h. The final composition of the feed ratio is as follows: 2.0 Na (Na) 2 O : 0.4 Al 2 O 3 : 5 SiO 2 : 0.0075 TPHAC : 0.015 CTAB : 150 H 2 And O. Then filtering, washing and drying 500 o C roasting 2 h to remove the template agent to obtain a sample Meso-NaY-1, and the structural parameters such as specific surface area and pore volume are listed in Table 1.
Example 2
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; then 0.397 g CTAB is added at 40 o Dissolving in 10.0 g of H under C 2 In O, under the temperature and stirring, 0.673 g TPHAC methanol solution with the concentration of 0.4382 g/g is dripped in 1 min, after 2 min of stirring, the TPHAC methanol solution is added into the silica sol system which is dispersed well, the mixture is quickly stirred for 10 min, the material is in a white solidification state, after 1 h is placed, 3.478 g NaAlO is added 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) and 4.840 g NaOH in 56.33 g H 2 Solution of O at room temperature (-25 ~) o C) Stirring 24 h, adding nano NaY molecular sieve seed crystal stock solution with total crystallized material mass fraction of 1.64% (2.31 g), stirring 4 h at room temperature, and 90 o C crystallized 46 h. The final composition of the feed ratio is as follows: 2.0 Na (Na) 2 O : 0.4 Al 2 O 3 : 5 SiO 2 : 0.0125 TPHAC : 0.025 CTAB : 150 H 2 And O. Then filtering, washing and drying 500 o C roasting 2 h to remove the template agent to obtain a sample Meso-NaY-2, and the structural parameters such as specific surface area and pore volume are listed in Table 1.
Example 3
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; then 0.556 g CTAB was added at 40 o Dissolving in 10.0 g of H under C 2 In O, the concentration of 0.942 g is completely dripped within 1 min under the condition of stirring at the temperature0.4382 Stirring a g/g TPHAC methanol solution for 2 minutes, adding the mixed solution into a silica sol system dispersed in the previous step at one time, quickly stirring for 10 min to obtain a white solidified material, standing the solidified material for 1 h, adding 3.478 g NaAlO 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) and 4.840 g NaOH in 56.33 g H 2 Solution of O at room temperature (-25) to o C) Stirring 24 h, adding nano NaY molecular sieve seed crystal stock solution with total crystallized material mass fraction of 1.64% (2.31 g), stirring 4 h at room temperature, and 90 o C crystallized 46 h. The final composition of the feed ratio is as follows: 2.0 Na (Na) 2 O : 0.4 Al 2 O 3 : 5 SiO 2 : 0.0175 TPHAC : 0.035 CTAB : 150 H 2 And O. Then filtering, washing and drying 500 o C roasting 2 h to remove the template agent to obtain a sample Meso-NaY-3, and the structural parameters such as specific surface area and pore volume are listed in Table 1.
Example 4
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; then 0.794 g CTAB is added at 40 o Dissolving in 10.0 g of H under C 2 In O, under the temperature and stirring, dripping 1.346 g TPHAC methanol solution with the concentration of 0.4382 g/g within 1 min, stirring for 2 min, adding the mixed solution into the previously dispersed silica sol system at one time, quickly stirring for 10 min to obtain a white solidified material, standing 1 h, adding 3.478 g NaAlO 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) and 4.840 g NaOH in 56.33 g H 2 Solution of O at room temperature (-25 ~) o C) Stirring 24 h, adding nano NaY molecular sieve seed crystal stock solution with total crystallized material mass fraction of 1.64% (2.31 g), stirring 4 h at room temperature, and 90 o C crystallized 64 h. The final composition of the feed ratio is as follows: 2.0 Na (Na) 2 O : 0.4 Al 2 O 3 : 5 SiO 2 : 0.025 TPHAC : 0.05 CTAB : 150 H 2 And O. Then filtering, washing and drying 500 o C roasting 2 h to remove the template agent to obtain a sample Meso-NaY-4, and the structural parameters such as specific surface area and pore volume are listed in Table 1.
Example 5
The silica sol (30%) was added beforehand to 42.48 g20.0 g H 2 O, fully stirring to ensure that the silica sol is well dispersed; then 0.198 g CTAB was added at 40 o Dissolving in 10.0 g of H under C 2 In O, under the temperature and stirring, 0.673 g TPHAC methanol solution with the concentration of 0.4382 g/g is dripped in 1 min, after 2 min of stirring, the TPHAC methanol solution is added into the silica sol system which is dispersed well, the mixture is quickly stirred for 10 min, the material is in a white solidification state, after 1 h is placed, 3.478 g NaAlO is added 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) and 4.840 g NaOH in 56.33 g H 2 Solution of O at room temperature (-25 ~) o C) Stirring 24 h, adding nano NaY molecular sieve seed crystal stock solution with total crystallized material mass fraction of 1.64% (2.31 g), stirring 4 h at room temperature, and 90 o C crystallized 46 h. The final composition of the feed ratio is as follows: 2.0 Na (Na) 2 O : 0.4 Al 2 O 3 : 5 SiO 2 : 0.0125 TPHAC : 0.0125 CTAB : 150 H 2 And O. Then filtering, washing and drying 500 o C roasting 2 h to remove the template agent to obtain a sample Meso-NaY-5, and the structural parameters such as specific surface area and pore volume are listed in Table 1.
Example 6
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; 0.595 g of CTAB were again added at 40 o Dissolving in 10.0 g of H under C 2 In O, under the temperature and stirring, 0.673 g TPHAC methanol solution with the concentration of 0.4382 g/g is dripped in 1 min, after 2 min of stirring, the TPHAC methanol solution is added into the silica sol system which is dispersed well, the mixture is quickly stirred for 10 min, the material is in a white solidification state, after 1 h is placed, 3.478 g NaAlO is added 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) and 4.840 g NaOH in 56.33 g H 2 Solution of O at room temperature (-25 ~) o C) Stirring 24 h, adding nano NaY molecular sieve seed crystal stock solution with total crystallized material mass fraction of 1.64% (2.31 g), stirring 4 h at room temperature, and 90 o C crystallized 80 h. The final composition of the feed ratio is as follows: 2.0 Na (Na) 2 O : 0.4 Al 2 O 3 : 5 SiO 2 : 0.0125 TPHAC : 0.0375 CTAB : 150 H 2 And O. Then filtering, washing and drying 500 o C roasting 2 h stripping dieThe plate agent was used to obtain a sample Meso-NaY-6, and the structural parameters such as specific surface area and pore volume are shown in table 1.
Example 7
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; then 0.542 g CTAB was added at 40 o Dissolving in 10.0 g of H under C 2 In O, under the temperature and the stirring, 0.919 g TPHAC methanol solution with the concentration of 0.4382 g/g is dripped in 1 min, after 2 min of stirring, the TPHAC methanol solution is added into the silica sol system which is dispersed well, the mixture is quickly stirred for 10 min, the material is in a white solidified state, after 1 h is placed, 3.466 g NaAlO is added 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) and 5.064 g NaOH in 56.33 g H 2 Solution of O at room temperature (-25 ~) o C) Stirring 24 h without adding nano NaY molecular sieve seed crystal stock solution, directly 90 o C crystallized 46 h. The final composition of the feed ratio is as follows: 2.0 Na (Na) 2 O : 0.4 Al 2 O 3 : 5 SiO 2 : 0.0175 TPHAC : 0.035 CTAB : 150 H 2 And O. Then filtering, washing and drying 500 o C roasting 2 h to remove the template agent to obtain a sample Meso-NaY-7, and the structural parameters such as specific surface area and pore volume are listed in Table 1.
Example 8
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; then 0.570 g CTAB was added at 40 o Dissolving in 10.0 g of H under C 2 In O, under the temperature and stirring, 0.967 g TPHAC methanol solution with the concentration of 0.4382 g/g is dripped in 1 min, after 2 min of stirring, the TPHAC methanol solution is added into the silica sol system which is dispersed well, the mixture is quickly stirred for 10 min, the material is white and solidified, after 1 h is placed, 3.490 g NaAlO is added 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) and 4.604 g NaOH in 56.33 g H 2 Solution of O at room temperature (-25 ~) o C) Stirring 24 h, adding nano NaY molecular sieve seed crystal stock solution with the total crystallization material mass fraction of 3.29% (4.736 g), stirring 4 h at room temperature, and 90 o C crystallized 46 h. The final composition of the feed ratio is as follows: 2.0 Na (Na) 2 O : 0.4 Al 2 O 3 : 5 SiO 2 : 0.0175 TPHAC : 0.035 CTAB : 150 H 2 And O. Then filtering, washing and drying 500 o C roasting 2 h to remove the template agent to obtain a sample Meso-NaY-8, and the structural parameters such as specific surface area and pore volume are listed in Table 1.
Example 9
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; then 0.556 g CTAB was added at 40 o Dissolving in 10.0 g of H under C 2 In O, under the temperature and stirring, 0.942 g TPHAC methanol solution with the concentration of 0.4382 g/g is dripped in 1 min, after 2 min of stirring, the TPHAC methanol solution is added into the silica sol system which is dispersed well, the mixture is quickly stirred for 10 min, the material is in a white solidification state, after 1 h is placed, 4.367 g NaAlO is added 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) and 4.396 g NaOH in 56.33 g H 2 Solution of O at room temperature (-25 ~) o C) Stirring 24 h, adding nano NaY molecular sieve seed crystal stock solution with total crystallized material mass fraction of 1.64% (2.31 g), stirring 4 h at room temperature, and 90 o C crystallized 46 h. The final composition of the feed ratio is as follows: 2.0 Na (Na) 2 O : 0.5 Al 2 O 3 : 5 SiO 2 : 0.0175 TPHAC : 0.035 CTAB : 150 H 2 And O. Then filtering, washing and drying 500 o C roasting 2 h to remove the template agent to obtain a sample Meso-NaY-9, and the structural parameters such as specific surface area and pore volume are listed in Table 1.
Example 10
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; then 0.556 g CTAB was added at 40 o Dissolving in 10.0 g of H under C 2 In O, under the temperature and the stirring, 0.942 g TPHAC methanol solution with the concentration of 0.4382 g/g is dripped in 1 min, after 2 min of stirring, the TPHAC methanol solution is added into the silica sol system which is dispersed before, the mixture is quickly stirred for 10 min, the material becomes white solidification, after 1 h is placed, 3.033 g NaAlO is added 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) and 5.062 g NaOH in 56.33 g H 2 Solution of O at room temperature (-25 ~) o C) Stirring 24 h, adding total crystalDissolving nano NaY molecular sieve seed crystal stock solution with mass fraction of 1.64% (2.31 g), stirring at room temperature for 4 h, and then stirring for 90 DEG o C crystallized 46 h. The final composition of the feed ratio is as follows: 2.0 Na (Na) 2 O : 0.35 Al 2 O 3 : 5 SiO 2 : 0.0175 TPHAC : 0.035 CTAB : 150 H 2 And O. Then filtering, washing and drying 500 o C roasting 2 h to remove the template agent to obtain a sample Meso-NaY-10, and the structural parameters such as specific surface area and pore volume are listed in Table 1.
Example 11 (control 1)
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, fully stirring to ensure that the silica sol is well dispersed; 1.588 g of CTAB were again added at 40 o Dissolving in 10.0 g of H under C 2 Adding into silica sol system, stirring for 10 min to obtain white solidified material, standing for 1 h, adding 3.478 g NaAlO 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) and 4.840 g NaOH in 56.33 g H 2 Solution of O at room temperature (-25 ~) o C) Stirring 24 h, adding nano NaY molecular sieve seed crystal stock solution with total crystallized material mass fraction of 1.64% (2.31 g), stirring 4 h at room temperature, and 90 o C crystallized 43 h. The final composition of the feed ratio is as follows: 2.0 Na (Na) 2 O : 0.4 Al 2 O 3 : 5 SiO 2 : 0.0 TPHAC : 0.1 CTAB : 150 H 2 And O. Then filtering, washing and drying 500 o C roasting 2 h to remove the template agent to obtain a reference sample Ref-NaY-1, and the structural parameters such as specific surface area, pore volume and the like are listed in Table 1.
Example 12 (control group 2)
20.0 g of H were added beforehand to 42.48 g silica sol (30%) 2 O, stirring thoroughly to disperse the silica sol well, 10.0 g of H 2 Adding 2.693 g TPHAC methanol solution with 0.4382 g/g into O, stirring for 2 min, adding into the dispersed silica sol system at one time, stirring rapidly for 10 min to obtain white solidified material, standing 1 h, adding 3.478 g NaAlO 2 (content: 0.5 g NaOH/g and 0.5 g Al 2 O 3 /g) and 4.840 g NaOH in 56.33 g H 2 Solution of O at room temperature (-25 ~) o C) Stirring 24 h, adding nano NaY molecular sieve seed crystal stock solution with total crystallized material mass fraction of 1.64% (2.31 g), stirring 4 h at room temperature, and 90 o C crystallized 43 h. The final composition of the feed ratio is as follows: 2.0 Na (Na) 2 O : 0.4 Al 2 O 3 : 5 SiO 2 : 0.05 TPHAC : 0.0 CTAB : 150 H 2 And O. Then filtering, washing and drying 500 o C roasting 2 h to remove the template agent to obtain a reference sample Ref-NaY-2, and the structural parameters such as specific surface area, pore volume and the like are listed in Table 1.
Figure 1
Using CTAB (2 mol%/SiO) only 2 ) The specific surface area and the volume of mesopores of a sample Ref-NaY-1 synthesized as a template are only 72.1 m 2 /g and 0.09 cm 3 The concentration/g is similar to that of the conventional microporous NaY molecular sieve, and the pure CTAB micelle does not have the capacity of inducing the NaY molecular sieve to form mesopores. The sample Ref-NaY-2 synthesized by only using 1 mol percent of TPHAC as a template has the mesoporous specific surface area and the mesoporous volume of 210 m 2 /g and 0.20 cm 3 The/g shows that the TPHAC molecule has the capacity of constructing hierarchical pores of the NaY molecular sieve. The Meso-NaY-2 sample synthesized by the method of example 2 of the present invention can have a specific surface area and a mesopore volume as high as 256 m when only 0.25 mol% of TPHAC and 0.5 mol% of CTAB are used, and the amount of TPHAC is 1/4 of that of Ref-NaY-2 of the control sample, as compared with the two control Ref-NaY-1 and Ref-NaY-2 samples 2 /g and 0.23 cm 3 The concentration/g is obviously larger than that of a Ref-NaY-2 sample, and the fact that TPHAC molecules are inserted in CTAB micelles is shown to greatly improve the capacity of inducing the molecular sieves to construct hierarchical pores. In particular, the Meso-NaY-3 sample synthesized by the method of example 3 of the invention can reach the mesopore specific surface area and the mesopore volume as high as 301.2 m when CTAB/TPHAC =2 and 0.35 mo% TPHAC amount is used 2 /g and 0.26 cm 3 The advantages presented by the process according to the invention are very clear.

Claims (16)

1. A method for synthesizing a hierarchical porous NaY molecular sieve is characterized by comprising the following steps: the hierarchical pore NaY molecular sieve adopts a mixed template agent containing amphiphilic organosilane and a cationic surfactant in the synthesis process, wherein the molar ratio of the amphiphilic organosilane to the cationic surfactant in the mixed template agent is 1 (0.1 to 5);
the amphiphilic organosilane is at least one of N, N-diethyl-N- [ 3-trimethylsilylpropyl ] hexadecylammonium bromide, N-diethyl-N- [ 3-trimethylsilylpropane ] hexadecylammonium iodide and N, N-dimethyl-N- [ 3-trimethylsilylpropyl ] octadecylammonium chloride;
the cationic surfactant is at least one of cetyl trimethyl ammonium bromide and cetyl trimethyl ammonium chloride;
the preparation method comprises the following steps:
(1) Firstly, uniformly mixing a silicon source, an aluminum source, an alkali source, a mixed template agent, water and a nano NaY molecular sieve seed crystal stock solution according to the calculated amount to finally form Na with the molar ratio of (0.35 to 0.5) 2 O:(0.06~0.1)Al 2 O 3: SiO 2 0.001 to 0.01, and (20 to 70) H 2 A sol of O; wherein the amount of the mixed templating agent is based on the moles of amphiphilic organosilane in the mixed templating agent;
(2) And (2) crystallizing, filtering, washing, drying and roasting the material obtained in the step (1) to obtain the hierarchical porous NaY molecular sieve.
2. The method of claim 1, wherein: the preparation process of the mixed template agent comprises the following steps: dissolving a proper amount of cationic surfactant in water, and adding the amphiphilic organosilane alcohol solution in a dropwise manner under the stirring condition of 20-50 ℃.
3. The method of claim 2, wherein: the preparation process of the mixed template agent is as follows: dissolving a proper amount of cationic surfactant in water, dropwise adding all required amphiphilic organosilane solutions into 30s-120s under the stirring condition of 20-50 ℃, and continuously stirring 60s-180s after the dropwise adding is optionally finished.
4. The method of claim 1, wherein: the specific preparation comprises the following steps:
(1) Firstly, uniformly mixing a silicon source, an aluminum source, an alkali source, a mixed template agent, water and a nano NaY molecular sieve seed crystal stock solution according to the metering to finally form Na with the molar ratio of (0.35 to 0.45) 2 O:(0.08~0.1) Al 2 O 3: SiO 2 0.0025 to 0.004, 20 to 40 percent of H 2 O; wherein the amount of the mixed templating agent is based on the moles of amphiphilic organosilane in the mixed templating agent;
(2) And (2) crystallizing, filtering, washing, drying and roasting the material obtained in the step (1) to obtain the hierarchical porous NaY molecular sieve.
5. The method of claim 4, wherein: in the step (1), a silicon source, an aluminum source, an alkali source, a mixed template agent, nano NaY molecular sieve seed crystal stock solution and water are uniformly mixed to form sol, wherein the addition amount of the nano NaY molecular sieve seed crystal stock solution accounts for 0.1-10% of the total mass of a sol system.
6. The method of claim 5, wherein: in the step (1), the addition amount of the nano NaY molecular sieve seed crystal stock solution accounts for 0.5-2% of the total mass of the sol system.
7. The method of claim 1, wherein: the molar ratio of the amphiphilic organosilane to the cationic surfactant in the mixed template agent is 1 (0.1 to 5).
8. The method of claim 7, wherein: the molar ratio of the amphiphilic organosilane to the cationic surfactant in the mixed template agent is 1 (0.5 to 5).
9. The method of claim 8, wherein: the molar ratio of the amphiphilic organosilane to the cationic surfactant in the mixed template agent is 1 (1~4).
10. The method of claim 9, wherein: the molar ratio of the amphiphilic organosilane to the cationic surfactant in the mixed template agent is 1 (2~3).
11. The method of claim 4, wherein: the mixing process in the step (1) is as follows: all silicon sources and part of H 2 And O, fully mixing and stirring, adding the required mixed template agent once or for multiple times, stirring until the material is white and solidified, standing for 0.5 to 2 hours, adding the required aluminum source and alkaline aqueous solution, stirring for a period of time, and then supplementing the balance of water.
12. The method of claim 11, wherein: the mixing process in the step (1) is as follows: all silicon sources and part of H 2 And O, fully mixing and stirring, adding the required mixed template agent once or for multiple times, stirring until the material is in a white solidified state, standing for 0.5 to 2 hours, adding the required aluminum source and alkaline aqueous solution, stirring at room temperature for 12 to 36 hours, adding the nano NaY molecular sieve seed crystal stock solution, and supplementing the balance of water.
13. The method of claim 4, wherein: the nano NaY molecular sieve seed crystal stock solution is prepared as follows: according to Na 2 O:Al 2 O 3 :SiO 2 :H 2 O = (10 to 15) = (10 to 18): 1 (200 to 400), mixing a silicon source, an aluminum source and water in an ice water bath at 0~5 ℃ to obtain a colorless transparent state, continuously stirring at room temperature for 12 to 36 hours, and then standing and crystallizing at 40 to 80 ℃ for 6 to 96 hours to obtain a semitransparent pale white viscous nano NaY molecular sieve seed crystal stock solution.
14. The method of claim 4, wherein: in the step (1), the silicon source is one or more of water glass, silica sol, silica gel and white carbon black; the aluminum source is one or more of aluminum nitrate, aluminum sulfate, sodium metaaluminate and metal aluminum; the alkali source is one or more of potassium hydroxide, sodium hydroxide and ammonia water.
15. The method of claim 4, wherein: in the step (2), the crystallization temperature is 80 to 100 ℃, and the crystallization time is 12 to 96 hours; the drying temperature is 100 to 150 ℃, the drying time is 2 to 5 hours, the baking temperature is 450 to 550 ℃, and the baking time is 2 to 4 hours.
16. A hierarchical pore NaY molecular sieve prepared by the method of any one of claims 1 to 15, characterized in that: the total specific surface area of the molecular sieve is 750-850 m 2 Per g, the total pore volume is 0.50 to 0.65 cm 3 (iv) g; the specific surface area of the mesopores is 120 to 320 m 2 The mesoporous volume is 0.15 to 0.25 cm 3 (ii)/g; the specific surface area of the micropores is 500 to 700 m 2 The pore volume of the micropores is 0.32 to 0.38 cm 3 /g。
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